Novel AgCl/Ag<Subscript>2</Subscript>CO<Subscript>3</Subscript> heterostructured photocatalysts with enhanced photocatalytic performance

A series of novel AgCl/Ag₂CO₃ heterostructured photocatalysts with different AgCl contents (5 wt%, 10 wt%, 20 wt%, and 30 wt%) were prepared by facile coprecipitation method at room temperature. The resulting products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS), respectively. The photocatalytic activity of the samples was evaluated by photocatalytic degradation of methyl orange (MO) under UV light irradiation. With the optimal AgCl content of 20 wt%, the AgCl/Ag₂CO₃ composite exhibits the greatest enhancement in photocatalytic degradation efficiency. Its first-order reaction rate constant (0.67 h^?1) is 5.2 times faster than that of Ag₂CO₃ (0.13 h^?1), and 16.8 times faster than that of AgCl (0.04 h^?1). The formation of AgCl/Ag₂CO₃ heterostructure could effectively suppress the recombination of the photo-generated electron and hole, resulting in an increase in photocatalytic activity.     

Bactericidal Effects of HVOF-Sprayed Nanostructured TiO2 on Pseudomonas aeruginosa

Titanium dioxide (TiO₂) has been shown to exhibit photocatalytic bactericidal activity. This preliminary study focused on examining the photocatalytic activity of high-velocity oxy-fuel (HVOF) sprayed nanostructured TiO₂ coatings to kill Pseudomonas aeruginosa. The surfaces of the nanostructured TiO₂ coatings were lightly polished before addition of the bacterial solution. Plates of P. aeruginosa were grown, and then suspended in a phosphate buffer saline (PBS) solution. The concentration of bacteria used was determined by a photo-spectrometer, which measured the amount of light absorbed by the bacteria-filled solution. This solution was diluted and pipetted onto the coating, which was exposed to white light in 30-min intervals, up to 120 min. It was found that on polished HVOF-sprayed coatings exposed to white light, 24% of the bacteria were killed after exposure for 120 min. On stainless steel controls, approximately 6% of the bacteria were not recovered. These preliminary results show that thermal-sprayed nanostructured TiO₂ coatings exhibited photocatalytic bactericidal activity with P. aeruginosa.     

室温水溶液法制备 Cu2O 纳米颗粒及其光催化性能

以乙酸铜为铜源,β-环糊精为表面活性剂,NaOH为添加剂,KBH4为还原剂,在室温水溶液中制备了直径约为50 nm的Cu2O,对产物的组成、能隙、光催化性能进行了分析。研究表明:产物结晶性良好,粒径分布较均匀,且产率高;此外,该纳米Cu2O由于比表面积大,对甲基橙在30 min内的催化效率高达94.9%,甲基橙几乎全部被降解,显示出良好的催化活性。     

Adsorption of copper ions on porous ceramsite prepared by diatomite and tungsten residue

In order to realize resource utilization of industrial tungsten residue and treatment of heavy metal wastewater in mining and metallurgical area of south China, a novel ceramsite was prepared with the main raw materials of diatomite and tungsten residue. The adsorption behavior of copper ions in solution on the ceramsite was investigated. Results indicated that the surface of the newly-developed ceramsite was rough and porous. There were lots of pores across the ceramsite from inner to outside. MnFe₂O₄ was one of the main components of the ceramsite. The Cu²⁺ adsorption capacity by the ceramsite reached 9.421 mg/g with copper removal efficiency of 94.21% at 303 K, initial Cu²⁺ concentration of 100 mg/L and dosage of 0.5 g after 300 min adsorption. With increase of ceramsite dosage, the total adsorption amount of Cu²⁺ increased, but the adsorption capacity decreased. The adsorption capacity increased with the increase of solution pH. The isothermal adsorption of Cu²⁺ by the ceramsite fitted the Freundlich model better. The adsorption mainly occurred on a heterogeneous surface, and was a favorable process. The adsorption process closely followed the pseudo-second kinetic equation. In initial stage of wastewater treatment, the adsorption process should be controlled mainly by diffusion, and the removal of Cu²⁺ can be improved by enhancing agitation.     

Preparation, characterization and photocatalytic activity of sulfuric acid-modified titanium-bearing blast furnace slag

The feasibility of reducing Cr(VI)from the aqueous solution by sulfuric acid-modified titanium-bearing blast furnace slag(SATBBFS)as a photocatalyst was investigated.The photocatalysts were examined by X-ray diffraction(XRD),UV-vis diffuse reflectance spectra,thermogravimetric analysis(TG)and Fourier transform infrared spectroscopy(FTIR).The photocatalytic activities of the different catalysts were evaluated by the photocatalytic reduction of Cr(VI)under UV-vis light irradiation.The results show that the photocatalytic activities of SATBBFS catalysts are strongly dependent on CaTiO3-to-TiO2 mass ratio,adsorption capacity and surface acidity,and SATBBFS calcined at 400°C shows a higher photocatalytic activity compared with other catalysts.     

Photocatalytic degradation of organic dyes with H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript>/TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript>

H₃PW₁₂O₄₀/TiO₂–SiO₂ was synthesized by impregnation method which significantly improved the catalytic activity under simulated natural light. The properties of the samples were characterized by Fourier transform infrared spectra (FTIR), X-ray powder diffraction pattern (XRD), Scanning electron micrographs (SEM), and Zeta potential. Degradation of methyl violet was used as a probe reaction to explore the influencing factors on the photodegradation reaction. The results show that the optimal conditions are as follows: initial concentration of methyl violet of 10 mg·L^?1, pH of 3.0, catalyst dosage of 2.9 g·L^?1, and light irradiation time of 2.5 h. Under these conditions, the degradation rate of methyl violet is 95.4 %. The reaction on photodegradation for methyl violet can be expressed as the first-order kinetic model, and the possible mechanism for the photocatalysis under simulated natural light is suggested. After used continuously for five times, the catalyst keeps the inherent photocatalytic activity for degradation of dyes. The photodegradation of methyl orange, methyl red, naphthol green B, and methylene blue was also tested, and the degradation rate of dyes can reach 81 %–100 %.     

Study of Reaction Mechanisms for Copper-Cobalt-Iron Sulfide Concentrates in the Presence of Lime and Carbon

The reaction mechanisms for the carbothermic reduction of complex mineral sulfide concentrates in the presence of lime were studied between 1073 K and 1323 K. The reaction mechanisms were studied by stopping the reduction experiments at different times and analyzing the reaction products by x-ray diffraction and scanning electron microscopy techniques. Magnetite (Fe₃O₄) and digenite (Cu_1.8S) were the initial phases formed during reduction of CuFeS₂ and Cu₅FeS₄ mineral particles, such that metallization of iron occurred before copper above 1173 K and at an equal stoichiometric ratio of CaO and C. The metallization of iron was found to take place via reduction of intermediate oxide phase (Fe₃O₄/FeO), whereas metallization of copper occurred via diffusion of S^2? ions away from the mineral particles or via formation of Cu-O-S liquid phase. Metallic iron and cobalt were embedded in the copper matrix due to a preferential reduction of iron and cobalt from the Cu-Fe-S and Cu-Co-S type of mineral particles. The effects of CaO/C ratio were analyzed and the rate of reactions was increasing with an increase in the CaO/C ratio. The formation of liquid phase has been discussed. The experimental results were found to be in good agreement with the thermodynamic predictions.     

Preparation of mesoporous titania particles using ionic liquid dissolving starch as templates

A mesoporous titania photocatalyst was prepared via calcining the solution of ionic liquid (1-methyl-3-butyl imidazolium bromide, [BMIM]Br) containing tetrabutyl titanate (TBT) and starch. The microstructure of the prepared mesoporous titania was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N₂ adsorption/desorption isotherm. The results indicate that the resulting mesoporous titania has a grain size of about 13.9 nm, a special surface area of 106 m²/g, and a pore volume of 0.22 cm³/g, and the pore size can be adjusted by the concentration of starch in ionic liquid. The photocatalytic activity of mesoporous titania in the degradation of methyl orange solution was determined. The effect of the specific surface area of mesoporous titania on the photocatalytic activity was also studied. The prepared mesoporous titania exhibits a high catalytic activity.     

Electrochemical performance of aluminum niobium oxide as anode for lithium-ion batteries

AlNbO_4,as lithium-ion batteries(LIBs) anode,has a high theoretical capacity of 291.5 m Ah g~(-1).Here,AlNbO_4 anode materials were synthesized through a simple solid-state method.The structure,morphology and electrochemical performances of AlNbO_4 anode were systematically investigated.The results show that AlNbO_4 is monoclinic with C2/m space group.The scanning electron microscopy(SEM) and transmission electron microscopy(TEM) characterizations reveal the AlNbO_4 particles with the size of 100 nm~(–2) lm.As a lithium-ion batteries anode,AlNbO_4 delivers a high reversible capacity and good rate capability.The discharge capacity is as high as 151.0 m Ah g~(-1)after 50 charge and discharge cycles at 0.1 C corresponding to capacity retention of 90.7 %.When the current density increases to 5.0C,AlNbO_4 anode displays reversible discharge capacity of 73.6 m Ah g~(-1)at the50 th cycle.     

Fe-MCM-41 from Coal-Series Kaolin as Catalysts for the Selective Catalytic Reduction of NO with Ammonia

Fe-MCM-41, one kind of high-ordered mesoporous materials catalysts, with molar ratio of Fe/Si = 0.01-0.1, was synthesized by hydrothermal method from coal-series kaolin. Fe-MCM-41 catalysts were characterized by Fourier transform infrared spectroscopy, high resolution transmission electron microscopy, N₂ adsorption-desorption, x-ray photoelectron spectroscopy, and UV-vis spectroscopy. The results clearly indicated that: (1) all the samples exhibited typical hexagonal arrangement of mesoporous structure; (2) the incorporation of tiny amount of Fe³⁺ onto the surface and pore channel of MCM-41 mesoporous materials could efficiently promote the deNO _x activity of these catalysts. Moreover, the Fe-MCM-41 mesoporous materials were evaluated in the selective catalytic reduction of NO with NH₃. The results showed that Fe-MCM-41 catalyst with Fe/Si = 0.05 showed the highest catalytic activity at 350 °C, a gas hourly space velocity of 5000 h^?1, n(NH₃)/n(NO) = 1.1, and O₂% = 2.5%.     

Effect of Cu2+ doping on photocatalytic performance of liquid flame sprayed TiO2 coatings

Cu²⁺ was added to liquid feedstock to deposit ion doping TiO₂ photocatalytic coatings through liquid flame spraying. The coating microstructure was characterized by x-ray diffraction (XRD), transmission electron microscopy, and x-ray photoelectron spectroscopy (XPS). The photocatalytic performance of coatings was examined by photodegradation of acetaldehyde. The XRD analysis shows that the crystalline structure of coatings is not significantly influenced by Cu²⁺ doping. The photocatalytic activity of the TiO₂ coatings is enhanced by Cu²⁺ doping. It is found that a high concentration of Cu²⁺ doping decreases the activity. The XPS analysis shows that the adsorbed oxygen concentration is increased with the increase of Cu²⁺ dopant concentration and decreases with a further increase of dopant concentration. The enhancement of photocatalytic activity can be attributed to the adsorption ability of oxygen and other reactants on the surface of doping TiO₂ coatings. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Plasma-Sprayed Photocatalytic Zinc Oxide Coatings

Fabrication of semiconductor coatings with photocatalytic action for photodegradation of organic pollutants is highly desirable. In this research, pure zinc oxide, which is well known for its promising photocatalytic activity, was deposited on stainless-steel plates by plasma spraying. The phase composition and microstructure of the deposited films were studied by x-ray diffraction analysis and scanning electron microscopy, respectively. Despite the low-energy conditions of the plasma spraying process, the zinc oxide coatings showed good mechanical integrity on the substrate. Their photocatalytic activity was evaluated using aqueous solution of methylene blue at concentration of 5 mg L^?1. The results showed the potential of the plasma spraying technique to deposit zinc oxide coatings with photocatalytic action under ultraviolet illumination. Ultraviolet–visible (UV–Vis) diffuse reflectance spectroscopy confirmed that the plasma spraying method could deposit zinc oxide films with higher photoabsorption ability relative to the initial powder.     

Structural,Microstructure, Mechanical and Electrical Properties of Porous Zr4+-Cordierite Ceramic Composites

Zirconium-cordierite ceramic composites have been synthesized by a co-precipitation method using MgCl₂·6H₂O, NaAlO₂, Na₂SiO₃·5H₂O, and ZrOCl₂·8H₂O as starting materials. XRD, FT-IR, and SEM techniques were employed to study the effect of zirconium on the crystal structure and microstructure of the samples. XRD results revealed that spinel MgAl₂O₄ and t-ZrO₂ phases were predominant in the samples with low Zr⁴⁺ content (10 wt.%), whereas zircon ZrSiO₄ was predominant with high Zr⁴⁺ content (≥15 wt.%). The densification behavior was improved from 30.4 to 44.6% of the theoretical density (2.6 g/cm³) at 15 wt.% of Zr⁴⁺. However, microhardness of the sintered samples was enhanced from 7.1 to 7.5 GPa with increasing the Zr⁴⁺ dose from 0 to 25 wt.%. On the other hand, the gradual increase in Zr⁴⁺ content from 0 to 25 wt.% led to suppression in the electrical resistivity (ρ) from 16.6 to 2.8 × 10⁹ Ω/cm, respectively. In addition, the dielectric permittivity (ε) of the pure cordierite was decreased with Zr⁴⁺ ion addition. The maximum dielectric permittivity (ε) at low frequencies (10 MHz) was 18.7 at 10 wt.% Zr⁴⁺ content, whereas at high frequencies (1 GHz) it was 38.8 at 15 wt.% Zr⁴⁺ content.     

Modeling of Ionic Conductivity Enhancement of LiClO4-PVA-C System by TiO2 Addition Using Complex Numerical Model of PDE

PVA-TiO₂ nanocomposite polymer electrolytes (PEs) were produced with different amounts of TiO₂ (0, 5, 10, 15, and 20 wt.%) using the electrospinning process. Morphological studies of PVA-TiO₂ nanofibers were accomplished with SEM. PVA-TiO₂ membranes exhibited a high porosity of 79-91%. The impedance results showed that incorporation of TiO₂ into the nanofiber membrane improved its ionic conductivity from 0.7 × 10^?5 to 2.5 × 10^?5 S/cm at room temperature. Nanofiber PEs showed very good reversibility and electrochemical stability up to 4.7 V. Diffusion coefficient of Li ion into PVA-TiO₂ nanocomposite PEs was estimated by using a complex numerical model of partial differential equation for evaluation of ion transmission. Diffusion coefficient of PVA-TiO₂ PEs containing different amounts of TiO₂ (0, 5, 10, 15, and 20 wt.%) increased with increasing the nanoparticles content.     

Oxidation Mechanisms of Copper and Nickel Coated Carbon Fibers

Differential-Thermal Analysis (DTA) and X-ray diffraction analysis were applied to determine the mechanisms of high-temperature oxidation of copper- and nickel-coated carbon fibers. Both kinds of coatings were deposited by electroless plating onto the fiber surface. The as-deposited copper film was crystalline, whereas the nickel coating consisted of an amorphous Ni–P alloy. Coated fibers were heated from room temperature to 900 °C in air at 10 °C min^?1. For the copper coating, the main oxidation product formed at low temperatures was Cu₂O, while at higher temperatures was CuO. The crystallization of Ni–P took place at 280–360 °C with the formation of Ni and Ni₃P. The final compounds were NiO, Ni₂P and Ni₃(PO₄)₂. After complete oxidation of the carbon fibers, copper and nickel-oxidized microtubes were obtained. Besides, while copper reduced the temperature of the fiber oxidation, nickel coatings increased the minimum temperature needed for this reaction.     

Microstructure and Thermomechanical Properties of Atmospheric Plasma-Sprayed Yb<Subscript>2</Subscript>O<Subscript>3</Subscript> Coating

In this study, a Yb₂O₃ coating was fabricated by the atmospheric plasma spray technique. The phase composition, microstructure, and thermal stability of the coating were examined. The thermal conductivity and thermal expansion behavior were also investigated. Some of the mechanical properties (elastic modulus, hardness, fracture toughness, and flexural strength) were characterized. The results reveal that the Yb₂O₃ coating is predominantly composed of the cubic Yb₂O₃ phase, and it has a dense lamellar microstructure containing defects. No mass change and exothermic phenomena are observed in the thermogravimetry and differential thermal analysis curves. The high-temperature x-ray diffraction results indicate that no phase transformation occurs from room temperature to 1500 °C, revealing the good phase stability of the Yb₂O₃ coating. The coefficient of thermal expansion of the Yb₂O₃ coating is (7.50-8.67)?×?10^?6 K^?1 in the range of 200-1400 °C. The thermal conductivity is about 1.5 W m^?1 K^?1 at 1200 °C. The Yb₂O₃ coating has excellent mechanical properties and good damage tolerant. The unique combination of these properties implies that the Yb₂O₃ coating might be a promising candidate for T/EBCs applications.     

Accelerated Oxidation of V2O5-Deposited Copper

The accelerated-oxidation kinetics of V₂O₅-deposited copper were studied in the temperature range 560?C800 °C in air. The accelerated oxidation followed the parabolic-rate law, indicating that the process was diffusion-controlled. Oxygen diffusion along liquid channels in the oxide scale was inferred to be the rate-limiting step in the overall mechanism. The parabolic-rate constant increased from 3.4 × 10^?6 to 1.6 × 10^?5 kg² m^?4 s^?1 with increasing the deposit mass from 0.075 to 0.225 kg m^?2 at 700 °C.     

A novel process for copper protection in the simulated industrial cooling water based on click synthesis and self‐assembling method

The triazole inhibitor of 1‐(p‐tolylthio)‐1H‐1,2,3‐triazole‐4‐carboxylic acid (TTC) was synthesized via the Cu(I)‐catalyzed azide‐alkyne 1,3‐dipolar cycloaddition reaction. The self‐assembling method was performed to fabricate the self‐assembled film of TTC on the copper surface. The electrochemical measurement results indicate that the TTC film can efficiently protect the copper from corrosion in high concentrated industrial cooling water. The protection efficiency of TTC film for copper is 92.2%. Surface characterizations imply that the copper with TTC film after corrosion is covered with multiple protective layers. It probably contains Cu(I) and Cu(II) complexes mixed with nitrogenous compound, Cl^? and SO₄^2?. The result of quantum chemical calculation shows that the superior performance of TTC film is related to the adsorption of TTC molecules on copper surface horizontally. This kind of adsorption is mainly achieved via the adsorption centers of triazole ring and O atoms in TTC molecule.     

Microstructure and photocatalytic activity of Ni-doped ZnS nanorods prepared by hydrothermal method

Pure ZnS and Ni²⁺-doped ZnS nanorods (Zn_1-xNi_xS, x=0, 0.01, 0.03, 0.05 and 0.07, mole fraction, %) were synthesized by hydrothermal method. The effects of Ni²⁺ doping on the phase-structure, morphology, elemental composition and optical properties of the samples were investigated by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), X-ray energy dispersive spectrometry (EDS) and ultraviolet-visible spectroscopy (UV-Vis), respectively. The photocatalytic activity of Zn_1-xNi_xS nanorods was evaluated by the photodegradation of organic dyes Rhodamine B (RhB) in aqueous solution under UV light irradiation. The results show that all samples exhibit wurtzite structure with good crystallization. The morphologies are one-dimensional nanorods with good dispersion, and the distortion of the lattice constant occurs. The band gap of Zn_1-xNi_xS samples is smaller than that of pure ZnS, thus red shift occurs. Ni²⁺-doped ZnS nanocrystals can enhance photocatalytic activities for the photodegradation of RhB. Especially, Zn_0.97Ni_0.03S sample exhibits better photocatalytic performance and photocatalytic stability for the decomposition of RhB.     

Effect of calcination temperature on microstructure and photocatalytic activity of BiOX (X=Cl,Br)

A series of BiOX (X=Cl, Br) were prepared by simple hydrolysis and then calcined at various temperatures and they were characterized by XRD, Raman, SEM, DSC–TGA, BET and UV–Vis. The photocatalytic activity was evaluated by photocatalytic degradation of methyl orange (MO) solution under simulated solar light irradiation. The results show that the phase structure, crystallite size, morphology, specific surface area, porous structure, and the absorption band-edges are related to the calcination temperature. For BiOBr, it has completely transformed to Bi₂₄O₃₁Br₁₀ at 600 °C and begins to transform to Bi₂O₃ at 800 °C. As for BiOCl, it begins to transform to Bi₂₄O₃₁Cl₁₀ at 600 °C and completely transforms to Bi₂₄O₃₁Cl₁₀ at 800 °C. Finally, the photocatalytic activity of BiOCl decreases with the temperature increasing owing to decrease of the specific surface areas and pore size, while the photocatalytic activity of BiOBr increases in the first stage and then decreases, which is related to good crystallization and three-dimensional structure.